Disazo triazine dyestuffs



United States Patent 3,340,247 DISAZO TRIAZINE DYESTUFFS Henri Riat, Arlesheim, and Karl Seitz, Neu-Allschwil,

Switzerland, assignors to Ciba Limited, Basel, Switzerland, a Swiss company No Drawing. Filed Sept. 8, 1965, Ser. No. 485,936 Claims priority, application Switzerland, Nov. 6, 1961,

12,841/61; Aug. 21, 1962, 9,949/62 8 Claims. Cl. 260-453) This is a continuation-in-part of our application Ser. No. 233,155, filed Oct. 25, 1962, now abandoned.

There are described in US. Patent No. 3,050,515, filed Mar. 16, 1959, by Raymond Gunst disazo dyestufis of the formula in which R and R each represent a benzene or naphthalene residue, R represents the residue of a naphthalene sulfonic acid bond to the azo bridge in 4-position and to the -NH-- group in l-position, and X represents a 2- amino-4-halogen-123:5-triazine nucleus. It is also mentioned in that specification that, in the manufacture of dyestuffs of the kind defined, 1-arnino-naphthalene-8-sulionic acid can be used to form the residue R It is an object of the present invention to provide disazo dyestuffs of this kind which yield cellulose dyeings having a higher stability of the fiber-dyestufi bond and a better fastness to chlorine especially a better fastness to the treatments with hypochlorite.

Other objects of the invention will become obvious from the following:

The present invention is based on the observation that specially valuable dyestufis can be obtained when diazo dyestuffs of the formula sOaH are prepared, in which R is a benzene or naphthalene residue more especially a benzene residue free from sulfonic acid groups or a sulfonaphthalene residue bound to the azo linkages in 1:4-position, X represents a mono-halogenated triazine residue, and n represents a whole positive number.

The disazo dyestuffs corresponding to the Formula 1a can be made by a condensing di-or tri-halogen-l:3:5-triazine with an aminodisazo dyestutt of the formula in such a manner that halogenated condensation products are formed.

The starting materials of the Formula 2 can be prepared by coupling a 1-amino-naphthalene-8-sulfonic acid such, for example, as 1:N-methylamino-naphthalene-8-sulfonic acid or 1-amino-naphthalene-8-sulfonic acid, which is not further substituted, with a diazotized aminoazo dyestuff that is prepared by coupling a diazotized aminobenzene disulfonic acid, for example, l-aminobenzene-2:5-disulfonic acid, with an amine of the benzene series, for example, the w-methane-sulfonic acid derivatives of aniline,

3,340,247 Patented Sept. 5, 1967 of ortho-methoxyaniline and of ortho-carboxy-aminobenzene (the w-methane sulfonic acid being split hydrolytically after the dyestuff has been made in order to liberate the amino group) and also meta-toluidine, 3-acetylaminol-aminobenzene, 3-butyrylamino-l-aminobenzene, 3-ureido-l-aminobenzene, l-amino 2 methyl-S-methoxybeuzene, l-amino-ZzS-dimethoxyor -diethoxybenzene, 1- amino-3-methoxybenzene, 1 amino-2-methoxy-5-isopropylbenzene, 1-arnino-2:S-dimethylbenzene or with 1- aminonaphthalene and more especially 1 aminonaphtha1ene-6-or -7-sulfonic acid.

The diazotized aminomonoazo dyestuffs used in preparing the aminodisazo dyestuffs of the Formula 2 given above may be obtained by known methods, for example, with the aid of mineral acids, especially hydrochloric acid, and sodium nitrite.

Coupling of the diazo compounds so obtained with the aforesaid l-aminonaphthalene sulfonic acids, that are capable of coupling in 4-position, can also be carried out by methods in themselves known.

The condensation of the starting dyestuffs so obtained with trihalogen-triazines, especially trichloro or tribromo- 1:3 :S-triazine or the mono-condensation products thereof (dihalogen-triazines) is advantageously carried out in the presence of an agent capable of binding acid, such as sodium acetate or sodium carbonate.

The monohalogen-triazine dyestuffs of the invention can also be made from dihalogen-triazine dyestuffs by substituting one of the two halogen atoms with an alkoxy or phenoxy group, but advantageously with an amino group, for example, by reaction with alcohols, phenols or ammonia or with a primary or secondary amine that advantageously has less than 13 carbon atoms. As amines of the kind defined there may be used, for example, methylamine, dimethylamine, ethylamine, diethylamine, propylamine, isopropylamine, butylamine, isobutylamine, hexylamine or cyclohexylamine, and also piperidine, morpho line, 'y-methoxy-propylamine, methoxyethylamine, ethanolamine, propanolamines, aniline, N-methylaniline, ortho-, metaor para-methylor methoxyaniline, ortho-, metaor para-aminobenzene sulfonic acid, aniline disulfonic acid, sulfonanthranilic acid, ortho-, metaor paraaminobenzoic acid, and also naphthylamine sulfonic acids, such as l-naphthylamine-6-sulfonic acid, 1- or 2- aminonaphthalenedior trisulfonic acids.

The condensation process of the invention is advantageously carried out in the presence of an agent capable of binding acid, such as sodium acetate, sodium carbonate or sodium hydroxide, and under such conditions that one exchangeable halogen atom remains in the finished product, that is to say, for example, in an organic solvent or at a relatively low temperature in aqueous medium.

In the manufacture of the dyestuffs of the invention by condensation of one of the aforesaid aminodisazo dyestufits with cyanuric chloride and with the more simple hydroxyl or amino compounds, at least the sequence of the condensation operations can generally be chosen as required. However, in some cases, it is advantageous to carry out the condensation with an alcohol or phenol before the condensation with the dyestufl The new dyestufis of the invention are suitable for dyeing or printing a very wide variety of materials, especially materials of fibrous structure that contain cellulose, for example, linen, regenerated cellulose and, more especially, cotton. They are specially suitable for dyeing according to the direct dyeing method from a relatively dilute bath and according to the pad-dyeing process, in which process the goods are impregnated with an aqueous dyestuif solution that may also contain salt and, after an alkali treatment, the dyestuffs are fixed, if necessary with the application of heat, that is to say, they are reacted with the fiber. This latter process and the direct dyeing method, by which many of the dyestuffs obtained by the process of the invention can also be applied, yield valuable dyeings that are fast to washing. Fast prints are obtained 4 at a moderately raised temperature. The dyestutf so obtained dyes cotton very fast red-brown tints.

EXAMPLE 2 b h ri i process 5 The same procedure is adopted as in Example 1. How- 1 Order t i r th t f t properties it i ever, after the condensation with cyanuric chloride, 50 advisable to submit the dyeings and prints so obtained Parts of all aqueous ammonia 501115011 f 10% Strength to a thorough rinse with cold water and hot water, if are added to the solution of dichloro-triazine dyestufi so necessary in the presence of a dispersing agent that asobtained, and the mixture iS heated 01 2 t0 3 hours at 30 1 1 th diff i f fi d dyestufi, to 40 C. The resulting monochloro-triazine dyestuif is Dyeings produced 01] poly-hydroxylated fibers espeeialthen salted 01111, filtered Off and dried. It dissolves in water 1y fibers containing cellulose, with the new dyestuffs are g a fed-brown Solution and y cotton y fast generally distinguished by a good fastness to light, and red-brown tints. more especially by an excellent fastness to washing and EXAMPLE 3 a very good fastness to chlorine.

If dyeing is carried out by the so-called catalyst process, To an aqueous Solutlon (lieutraihzed Wlth Sodium in which the fixation of the dyestuffs on the fiber is bonate) Paris of an aimno'dlsazo i i q achieved by means of tertiary amines such, for example, Coupling dlaz'onzed bammobenzerie'zzij'disulfomc acld as triethylamine or dicyclo-(2:2:2)-triethylene-diamine i Himmo'naphthalene further dlazqtlzailori and 6011' (aza-dicyclo-octane) or with other basic compounds, for phngwlth 1.'am1.n0naphtha1ene'8'Sulfomc a weak example, N:N dimethy1 hydrazine, if necessary, Without 1y acid medium 18 added a neutral aqueous solution of the the application of heat, the fixation reaction is accelerated pnmary iondensiitlon Product obtamed q parts in the case of the dyestufis of the invention, and thus of cyaimnqchlonde and 3 of l'ammobenzene'?" deeper dyeings can be obtained in a Shorter time. sulfomc acid, and the whole 15 stn red for a few hours The following examples illustrate the invention. Unat a p betw'aien 40 and 60 m whlch.p.rocess less otherwise stated, the parts and percentages are by the.react1n k neutral by the addmon of weight: a dilute solution of Sodium carbonate. When the pH EXAMPLE 1 value remains constant the dyestutf 1s salted out, filtered off and dried. It dyes cotton fast red-brown tints.

19 parts of cyanuric chloride are finely dispersed in 300 If there is used as condensation agent the primary parts of ice water. To the dispersion so obtained is added condensation product obtained from cyanuric chloride and a solution of 72.1 parts of an amino-disazo dyestuff, pre- 1-aminobenzene-2-sulfonic acid or 1-amino-benzene-2z5- pared by coupling the diazo-compound prepared from 1- disulfonic acid, there are obtained dyestuffs with similar aminobenzene-ZzS-disulfonic acid with l-aminonaphthalproperties. ene-6-sulfonic acid, further di'azotizing the resulting If there is used as condensation agent the correspondaminoazo-dyestuif and coupling with l-amino-naphthaling proportion of 6-phenoxy-2z4-dichloro-1c3z5-triazine ene-8-sulfonic acid in a slightly acid medium (pH 4 to 5), or 6-methoxy-2-z4-dichloro-1:315-triazine or fi-phenylthioin 500 parts of water, which solution is neutralized with 2:4-dichloro-1:3:5-triazine, there are obtained dycstufis sodium carbonate. The whole is stirred for 2 hours at 5 that likewise dye cotton fast red-brown tints. to 8 C. and the pH value of the solution is kept between 40 In the following table there are listed further examples 5 and 7 by the gradual addition of a dilute sodium hyof dyestuffs that are obtained when the disazo dyestuffs droxide solution. When the condensation is terminated, obtained from the components listed in columns I to III the resulting dichlorotriazine dyestuti is salted out, filtered are condensed with cyanuric chloride and the dichloroo'tf, the paste is mixed with a concentrated aqueous solutriazine derivatives so obtained are, if necessary, reacted tion of 4 parts of mono-sodium phosphate and 4 parts of with the compounds listed in column 1V. Column V shows di-sodium phosphate, and the mixture is dried in vacuo the tints obtained with the dyestuffs so obtained.

TABLE I II r v v l-gfiiinobenzene-fi-disulfonic Meta-toluidine 1-:I1niinonaphthalene-8-su1f nje Ammonia Brown i) Aniline 1- 1-5515taaiarassironz'"' fifiil'ifffi 8: l-grsuinobenzene-2z5-disulfonic D0,

D0 B-hydroxyethylamiue Do.

Do 1-aminobenzene-3-sulionic Do.

-..- M i hhnlinp D0.

D9. Diefhannlarnine Do,

Do N-methylaniline Do.

D0 l-aiill'luggr-fe-methoxy-dmethylfl Ar 'r ir vi ri i Reddish brown,

D0 1-amino-2:fidimethylbenzene. r1n orangebmwn' l-aaigfiinobenzenee -1 D0- l-a i glaterz'es staasafiaua"" ;y @a-tammo 1-33 333; ffiiff; 35331 1 Dn d o Ammonia Do.

: ilfitfifi z iiigii fih 31:33:33: "1:3:"32 ":1 iij bmwn aminobenzene. AmlmP l-gfiiggfiapEhalene-ty do Orange-brown. 3-methoxyaniline-.. -d0 do Do. l-agmlilrzxggidduuethoxy do -do Red-brown.

TABLEContim1ed I II III IV V l-aminobenzene zddisulionie l-aminonaphthalene-7-sul- 1-aminonaphthalene-8-sull-aminobenzene-Zi-sulfonie Do.

acid. ionic ac ionic acid. 2.01

Do do .do Ammonia Do, Do Commercial mixture of 1- do do Do.

aminonaphthalene-B- and 7-sulionic acid. l-aminobenzene-Z:4-disulionic l-aminonaphthalene-fi-suldn (in D0.

ac tonic acid. l-arniinobenzene-azfi-disulionic do do Do.

acl

Do do Ammonia Do. l-ann'finobenzeue-Zzfi-disulfonie l-aminonaphthalene do do aci Dn dn do 1-a1ninobenzene-3:5-disulionic Do.

ac D l-aminnnaphfh lflflP-(i-suldo Phpnnl Do.

ionic acid. Do do .do l-hydoxybenzene-et-sulionic Do.

aci Do do do B-hydroxypropylamine Do. Do do do 3-rnethoxypropylamine Do. Do dn do 4-aeetylamino-1-amino- D0.

benzene. Do do do 2-hydroxy-5-aminobenzoic Do.

EXAMPLE 4 25 in which R represents a member selected from the group 62 parts of the amino-disazo dyestutf (2:5-aniline-disulfonic acid-+1 amino 2: S-dimethylbenzene l-aminonaphthalene-8-sulfonic acid) are dissolved in 1000 parts of water, and the solution so obtained is neutralized with sodium carbonate. The solution is heated to 60 C. and to it is added a solution of 22 parts of 2:425:6-tetra-chlorpyrimidine in 80 parts of acetone. The mixture is stirred for 12 hours at 80 C., and is kept slightly acidic to neutral by the addition of a dilute solution of sodium hydroXide. The resulting trichloropyrimidyl derivative is salted out, filtered 0E and dried. It dyes cotton fast brown tints.

If the 2:4:5:6-tetra-chlorpyrimidine is replaced by 2:4:6-trichlorpyrimidine, there is obtained a dyestuff with similar properties.

Dyeing prescription 2 parts of the dyestufi' prepared in the manner described in Example 1 are dissolved in 100 parts of water. A cotton fabric is impregnated on a padding mangle at room temperature with the cold dyestufi solution, and the excess dye-liquor is squeezed out in such a manner that the material retains 75% of its weight of dyestuif solution.

The cotton impregnated in this manner is dried and then impregnated at room temperature with a solution that contains, per liter, parts of sodium hydroxide and 300 parts of sodium chloride. The cotton is then squeezed to a liquor uptake of 75 and then steamed for 60 seconds at 100 to 101 C. The material is then rinsed, treated in a sodium bicarbonate solution of 0.5% strength, rinsed, soaped at the boil for hour in a 0.3% solution of a non-ionic detergent, rinsed again and then dried. There is obtained a red-brown dyeing that is fast to Washing and light.

For testing the fiber-dyestutf stability one part of dyeing may be treated for /2 hour with 40 parts of an aqueous solution containing per liter g. of acetic acid, mixed with cold and warm Water and dried. The alteration (less of strength) of the dyeing is proportional to the instability of the bond.

What is claimed is:

1. A water-soluble disazo dyestuif of the formula consisting of a benzene and a naphthalene radical that is bound to the azo groups in l-position and 4-position, said benzene radical being selected from the group consisting of the unsubstituted 1,4-phenylene and the benzene radicals containing a substituent selected from the group consisting of lower alkyl, acetylamino and lower alkoxy and the naphthalene radical being selected from the group consisting of the 1,4-naphthalene and the sulfonaphthylene radicals, n represents a whole number from 1 to 3, and X represents a mono-chloro trazine nucleus and further substituted by groups selected from the class consisting of chloro, lower alkoxy, phenoxy, sulfo-phenoxy, phenylthio, amino, hydroxy lower alkylamino, lower alkoxyalkylamino, phenylamino, monosulfophenylamino, disulfophenylamino, carboxyphenylamino, morpholino, N-lower alkyl-N-phenylamino, N-lower alkyl-N-sulfophenylamino and acetylamino-aminobenzene.

2. A disazo dyestuft of the formula :N N=N NH-X in which one Z represents hydrogen and the other Z represents a sulfonic acid group, and X represents 4-amino- 2-chloro-l:3:5-triazine residue bound to the NH- group in 6-position.

3. A disazo dyestuif of the formula SOaH SOaH

in which R represents 1:4-phenylene radical and X represents 4-amino-2-chloro-l:3:S-triazine residue bound to the NH- group in 6-position.

7 4. A disazo dyestufi of the formula S'O3H =N-R-N=N NHX 10 in which R is xylidine radical bound to the am group in the 1- and 4-positions, and X is 4-amino-2-chloro-1z3s5- triazinyl group bound to the -NH- group in 6-position.

5. The dyestuff of the formula 1 r 5 SO H CH /C\ I a r H =NC N=N NH-C C-NHa O CH3 SOQH SOaH 6. The dyestufi of the formula 25 I 30311 %O\ 1 R =N N=N NH-C CNH2 30 OH; SOaH SOsH 8 7. The dyestuff of the formula 503E %C\ ]-N=N N=N NHC O-NH:

N SO H sfoarr s og]:

8. The dyestuff of the formula 01 3 7 I, SOaH /C\ r N=N N=N NH-C C-NH:

SOaH s og]; 950311 I References Cited UNITED STATES PATENTS 2,945,022 7/1960 Fasciati et a1. 260153 3,038,893 6/1962 Andrew 260-453 X 3,050,515 8/1962 Gunst 260153 3,057,844 10/1962 Andrew et a1. 260-153 3,057,846 10/1962 Andrew et a1 260-153 X CHARLES B. PARKER, Primary Examiner.

JOSEPH P. BRUST, Examiner.

D. M. PAPUGA, Assistant Examiner. 

1. A WATER-SOLUBLE DISAZO DYESTUFF OF THE FORMULA 